US4877762A - Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons - Google Patents
Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons Download PDFInfo
- Publication number
- US4877762A US4877762A US07/234,804 US23480488A US4877762A US 4877762 A US4877762 A US 4877762A US 23480488 A US23480488 A US 23480488A US 4877762 A US4877762 A US 4877762A
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- United States
- Prior art keywords
- catalyst composition
- silica
- group
- catalyst
- refractory oxide
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- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
Description
TABLE I ______________________________________ Typical Dear- Hydro- Raw Deashed senated treated Shale Shale Shale Shale Oil Oil Oil Oil ______________________________________ Pour Point, °F. 50-65 50-65 50-70 65-90 Sulfur, wt. % as S 0.5-1.5 0.5-1.5 0.2-1.0 0.003-0.2 Nitrogen, wt. % as N 1.6-2.2 1.6-2.2 1.4-2.0 0.020-0.350 Arsenic, wppm as As 40-70 20-30 <1 <1 ______________________________________
TABLE II ______________________________________ FEEDSTOCK AND PRODUCT COMPOSITION AND PROPERTIES Feed- stock ______________________________________ Product -- A-2 A-4 A-11 A-18 A-25 A-39 A-41 Sample Designation Days into -- 2 4 11 18 . 25 39 41 Run Gravity, 35.0 37.3 36.0 37.3 37.2 37.5 36.7 37.6 ° API Pour Point, +80 +5 +15 +20 +20 +10 -5 +5 °F. Viscosity at 6.50 4.526 5.320 4.818 4.886 4.421 5.155 4.225 100° F. cSt Viscosity at 3.84 2.863 3.273 3.020 3.046 2.857 3.185 2.709 140° F. cSt Nitrogen, 900 179 184 197 197 165 184 179 wppm Sulfur, 41 16 15 7 15 10 15 16 wppm Simulated Distillation Vol. % Boiling Under 80° F. 0 1.03 0.44 0.84 1.07 1.14 0.37 0.47 300° F. 4.06 10.25 7.69 9.03 9.08 11.16 9.04 10.32 520° F. 32.91 41.94 37.82 40.67 39.31 43.01 38.87 44.35 670° F. 56.09 65.74 62.82 64.34 63.18 65.71 62.53 67.01 750° F. 68.05 76.57 74.17 75.13 74.39 76.21 73.92 77.08 ______________________________________
TABLE III ______________________________________ Properties and Characteristics of Feedstock ______________________________________ Gravity, ° API @ 60° F. 21.3 Distillation, D-1160, °F. Pour Point, °F. 55 IBP/5 210/377 Viscosity @ 100° F., SUS 154.2 10/20 446/535 Viscosity @ 140° F., SUS 71.4 30/40 614/692 Sulfur, wt. % 0.835 50/60 760/817 Nitrogen, Total, wt. % 1.80 70/80 869/929 Hydrogen, wt. % 11.61 90/95 1000/1047 Total Olefins, wt. % 18.8 Max/Rec. 1081/97.6 Aniline Point, °C. 40.3 Arsenic, wppm 0.7 Oxygen, wppm 119 ______________________________________
TABLE IV ______________________________________ Product Sulfur, Nitrogen, and Pour Point Operating Temperature, Pour Point °F. Nitrogen, wppm Sulfur, wppm °F. A B C A B C A B C ______________________________________ 749 -- -- 80 -- -- 1230 -- -- 107 760 65 75 -- -- 165 -- 773 46 -- 780 70 75 80 465 55 84 50 46 30 800 -10 75 -- 118 9 -- 23 23 -- 810 -- - 55 -- -- 5 -- -- 18 820 -50 70 -- -- 4 -- 22 22 -- ______________________________________
TABLE V ______________________________________ Hydro- Simultaneous Hydro- Condition treating treating-Hydrodewaxing ______________________________________ Space Velocity, LHSV Suitable 0.1-2.0 0.1-10 Preferred 0.3-0.7 0.5-2.0 Temperature, °F. Suitable >650 >650 Preferred 700-775 700-780 Highly Preferred 725-745 720-750 Pressure, psig Suitable >750 >750 Preferred 1500-2500 1500-3000 Highly Preferred 2000-2500 2000-2500 H.sub.2 Added Plus H.sub.2 in Recycle Gas, scf/bbl Suitable >500 >500 Preferred >2000 1500-15,000 Highly Preferred 4000-7000 6000-10,000 ______________________________________
TABLE VI ______________________________________ Gravity, ° API 25.1 Modified Vacuum Engler Distillation, Volume Percent Hydrogen, wt. % 11.95 Cut Versus Temperature, °F. Nitrogen, kjel, wt. % 1.75 IBP/5 233/346 Sulfur, X-ray, wt. % 0.409 10/20 400/532 Oxygen, wt. % 0.842 30/40 615/693 Analine Point, °F. 121 50/60 758/814 Pour Point, °F. +76 70/80 871/922 Viscosity @210° F., 38.2 90/95 981/1025 SSU Carbon Residue, D189, 0.5 EP at 98.7% 1072 wt. % ______________________________________
TABLE VII ______________________________________ Hydro- Hydrotreating- treating Dewaxing ______________________________________ Pressure, psig 2225 2225 Space Velocity, LHSV 0.59 1.0 Reactor Temperatures, °F. 715-735 740-780 Catalyst Charge, gm 431 300* Gas Rate, scf/bbl 5500 8000 H.sub.2 Concentration in Gas, mole % 91 91 ______________________________________ *Note: During a portion of the run, the catalyst charge also contained, at the bottom of the bed, 30 grams of Catalyst B.
TABLE VIII ______________________________________ Average Bed Reactor 745 760 780 Temperature, °F. Pour Point, °F. +25 0 -25 Maximum JP-4*: TBP Cuts, °F. C.sub.5 -480 C.sub.5 -480 C.sub.5 -510 Yield, vol. % 34 42 52 Heavy Diesel: TBP Cuts, °F. 480-620 480-640 510-620 Yield, vol. % 25 29 20 Fuel Oil: TBP Cuts, °F. 620+ 640+ 620+ Yield, Vol. % 49 33 28 Light Naphtha: TBP Cuts, °F. C.sub.5 -280 C.sub.5 -270 C.sub.5 -270 Yield, vol. % 8 8 10 Maximum Diesel: TBP Cuts, °F. 280-680 270-720 270-760 Yield, vol. % 61 73 78 Oil: TBP Cuts, °F. 680+ 720+ 780+ Yield, vol. % 35 23 12 ______________________________________ *Note: JP4 fractions obtained when the hydrotreatinghydrodewaxing reactor contained 30 gm. of Catalyst B consistently met the JFTOT stability test, ASTM D3241-77 entitled "Test for Thermal Oxidation Stability of Aviation Turbine Fuels.
TABLE IX ______________________________________ Gravity, ° API 35.0 ASTM Distillation, D-1160 Pour Point +80 Initial BP 223° F. Kinematic Viscosity 10% 394° F. at 100° F., cSt 6.50 50% 660° F. at 100° F., SUS 47.2 90% 914° F. Nitrogen, wppm 900 EP 1027° F. Sulfur, wppm 41 ______________________________________
TABLE X ______________________________________ Average Bed Reactor Temperature to Yield +30° F. Pour Point Catalyst Dewaxing Component Product ______________________________________ A ZSM-5; 3.0 wt. % A1.sub.2 O.sub.3 747° F. B Silicalite; 0.74 wt. % A1.sub.2 O.sub.3 739° F. C Silicalite; 0.6 wt. % A1.sub.2 O.sub.3 743° F. D Silicalite; 0.44 wt. % A1.sub.2 O.sub.3 745° F. E Silicalite; 0.0044 wt. % A1.sub.2 O.sub.3 797° F. ______________________________________
TABLE XI ______________________________________ Gravity, ° API 29.1 ASTM Distillation, D-1160, ° F. Pour Point, ° F. 102 IBP 660 Wax, wt. % 18.0 5% 726 Sulfur, wt. % 0.053 10% 748 Nitrogen, wt. % 0.014 30% 793 Kinematic Viscosity 50% 841 at 140° F., cSt 25.47 70% 929 at 210° F., sCt 8.395 90% 1065 ______________________________________
Claims (54)
______________________________________ d-A Relative Intensity ______________________________________ 11.1 ± 0.2 VS 10.0 ± 0.2 VS 3.85 ± 0.07 VS 3.82 ± 0.07 S 3.76 ± 0.05 S 3.72 ± 0.05 S ______________________________________
______________________________________ d-A Relative Intensity ______________________________________ 11.1 ± 0.2 VS 10.0 ± 0.2 VS 3.85 ± 0.07 VS 3.82 ± 0.07 S 3.76 ± 0.05 S 3.72 ± 0.05 S ______________________________________
______________________________________ d-A Relative Intensity ______________________________________ 11.1 ± 0.2 VS 10.0 ± 0.2 VS 3.85 ± 0.07 VS 3.82 ± 0.07 S 3.76 ± 0.05 S 3.72 ± 0.05 S ______________________________________
______________________________________ d-A Relative Intensity ______________________________________ 11.1 ± 0.2 VS 10.0 ± 0.2 VS 3.85 ± 0.07 VS 3.82 ± 0.07 S 3.76 ± 0.05 S 3.72 ± 0.05 S ______________________________________
______________________________________ d-A Relative Intensity ______________________________________ 11.1 ± 0.2 VS 10.0 ± 0.2 VS 3.85 ± 0.07 VS 3.82 ± 0.07 S 3.76 ± 0.05 S 3.72 ± 0.05 S ______________________________________
______________________________________ d-A Relative Intensity ______________________________________ 11.1 ± 0.2 VS 10.0 ± 0.2 VS 3.85 ± 0.07 VS 3.82 ± 0.07 S 3.76 ± 0.05 S 3.72 ± 0.05 S ______________________________________
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/234,804 US4877762A (en) | 1981-05-26 | 1988-08-22 | Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/267,247 US4428862A (en) | 1980-07-28 | 1981-05-26 | Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons |
US07/234,804 US4877762A (en) | 1981-05-26 | 1988-08-22 | Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons |
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Application Number | Title | Priority Date | Filing Date |
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US06/267,247 Division US4428862A (en) | 1980-07-28 | 1981-05-26 | Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons |
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US4877762A true US4877762A (en) | 1989-10-31 |
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US07/234,804 Expired - Fee Related US4877762A (en) | 1981-05-26 | 1988-08-22 | Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5246568A (en) * | 1989-06-01 | 1993-09-21 | Mobil Oil Corporation | Catalytic dewaxing process |
US5977425A (en) * | 1994-11-22 | 1999-11-02 | Exxon Research And Engineering Co | Method for upgrading waxy feeds using a catalyst comprising mixed powdered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle |
US20090288994A1 (en) * | 2004-04-28 | 2009-11-26 | The Governors Of University Of Alberta | Process for extraction of bitumen from oilsands |
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Pulsed Proton Nuclear Magnetic Resonance Study of Water Mobility in Pentasils ZSM 5 and Silicalite by Maidwald et al. set forth in Proceedings of the Fifth International Conference on Zeolites, edited by Dr. L. V. C. Rees, Jun. 2 6, 1980, pp. 562 to 570. * |
Reactions on ZSM 5 Type Zeolite Catalysts by Anderson et al. in Journal of Catalysis, vol. 58, pp. 114 to 130 (Jun. 15, 1979). * |
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Research Articles Triggers Dispute on Zeolite by Budiansky set forth in Nature, vol. 300, Nov. 25, 1982, p. 309. * |
Resolving Crystallographically Distinct Tetrahedral Sites in Silicalite and ZSM 5 by Solid State NMR by Fyfe et al., set forth in Nature, vol. 296, Apr. 8, 1982, p. 530. * |
Silicalite 2, a Silica Analogue of the Aluminosilicate Zeolite ZSM 11 by Bibby et al. in Nature, vol. 380, pp. 664 to 665, Aug. 23, 1979. * |
Silicalite, a New Hydrophobic Crystalline Silica Molecular Sieve by Flanigen et al. in Nature, vol. 271, pp. 512 to 516, Feb. 9, 1978. * |
Synthetic Crude Oil and Transportation Fuels from Shale Oil by Randle et al., American Petroleum Institute, 46th Midyear Refining Meeting, May 14, 1981. * |
When is a Zeolite not a Zeolite by Rees set forth in Nature, vol. 296, Apr. 8, 1982, pp. 491 to 492. * |
Zoned Aluminum Distribution in Synthetic Zeolite ZSM 5 by Ballmoos et al. in Nature, vol. 289, Feb. 26, 1981, pp. 782 and 783. * |
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